Chemical mechanical polishing slurries and cleaners containing salicylic acid as a corrosion inhibitor

ABSTRACT

The invention provides methods for CMP polishing, residue removal and post-CMP polishing of a metal containing substrate. The CMP polishing methods for contacting a metal-containing substrate with a composition comprising an oxider, a salicylic acid compound, water, and an abrasive. The post-CMP polishing and residue removal methods require contacting a metal-containing substrate with a composition comprising an oxidizer, a salicylic acid compound, and water.

FIELD OF THE INVENTION

The invention relates to compositions and methods forchemical-mechanical polishing/planarization and/or post-CMP cleaning ofmetal-containing substrates with a composition containing an oxidizerand an organic or inorganic acid, and more particularly to compositionsand methods for chemical-mechanical polishing/planarization and/orpost-CMP cleaning of copper-containing substrates used in integratedcircuit manufacture.

BACKGROUND OF THE INVENTION

Chemical-mechanical polishing or planarization (CMP) processes arewell-known. See, for example, Chemical Mechanical Polishing in SiliconProcessing, Semiconductors and Semimetals, Vol. 62, Edited by Li, S. etal., which is expressly incorporated herein by reference. Also directlyincorporated by reference for all purposes are the following commonlyassigned patents:

-   -   U.S. Pat. No. 5,891,205 to Picardi et al., which issued on Apr.        6, 1999, entitled Chemical Mechanical Polishing Composition;    -   U.S. Pat. No. 5,981,454 to Small, which issued on Nov. 9, 1999,        entitled Post Clean Treatment Composition Comprising An Organic        Acid And Hydroxylamine;    -   U.S. Pat. No. 6,117,783 to Small et al., which issued on Sep.        12, 2000, entitled Chemical Mechanical Polishing Composition And        Process;    -   U.S. Pat. No. 6,156,661 to Small, which issued on Dec. 5, 2000,        entitled Post Clean Treatment;    -   U.S. Pat. No. 6,235,693 to Cheng et al., which issued on May 22,        2001, entitled Lactam Compositions For Cleaning Organic And        Plasma Etched Residues For Semiconductor Devices;    -   U.S. Pat. No. 6,248,704 to Small et al., which issued on Jun.        19, 2001, entitled Compositions For Cleaning Organic And Plasma        Etched Residues For Semiconductors Devices;    -   U.S. Pat. No. 6,251,150 to Small et al., which issued on Jun.        26, 2001, entitled Slurry Composition And Method Of Chemical        Mechanical Polishing Using Same;    -   U.S. Pat. No. 6,313,039 to Small et al., which issued on Nov. 6,        2001, entitled Chemical Mechanical Polishing Composition And        Process; and    -   U.S. Pat. No. 6,498,131 to Small et al., which issued on Dec.        24, 2002, entitled Composition For Cleaning Chemical Mechanical        Planarization Apparatus.

CMP processes are commonly used to polish or “planarize” the surfaces ofwafers at various stages of fabrication to improve wafer yield,performance and reliability. In CMP, typically the wafer is held inplace on a mount using negative pressure, such as vacuum, or hydrostaticor pneumatic pressure. The mount is typically situated over a polishingpad. CMP generally involves applying a polishing composition or slurryto the polishing pad, establishing pressure-contact between thecomposition- or slurry-coated wafer surface and the polishing pad whileproviding relative motion, typically rotational or orbital motion,between the wafer surface and the polishing pad.

The polishing composition typically contains an abrasive material, suchas silica, ceria, and/or alumina particles, in an acidic, neutral, orbasic solution. Merely by way of example, a polishing composition usefulin the CMP of tungsten material on a substrate may contain abrasivealumina, also called aluminum oxide, an oxidizing agent such as hydrogenperoxide, and either potassium hydroxide or ammonium hydroxide. A CMPprocess employing such a polishing composition may provide a predictablerate of polishing, while largely preserving desirable features on thewafer surface.

For such a semiconductor wafer, a typical CMP process involves polishingthe metal in a controlled manner to preferentially etch certainconductors, insulators or both over the the oxide beneath the metal,such that the metal is substantially coplanar with the oxide and remainsin the grooves or stud vias of the oxide. After CMP, the substantiallycoplanar surface is ready for further processing. CMP is currently theprimary method used to polish or “planarize” wafers in back end of theline (BEOL) processes.

Semiconductor fabrication processes such as photolithography haveevolved significantly, such that advanced devices having very fineoxide, metal, and other surface features, with sub-0.25 microngeometries (such as 0.18 micron or less), are now being made. Processtolerances are necessarily tighter for these advanced devices, callingfor improvements in CMP technology to obtain desired material removalrates while minimizing wafer defects or damage. A variety of approacheshave been taken in an effort to improve CMP processes to improveplanarity.

On the other hand, economic forces are requiring the use of fasterprocessing. One approach has involved increasing the downward pressureon the wafer carrier in order to increase material removal rates. Thisapproach is generally disfavored as the requisite downward pressure isconsidered too high and too likely to cause wafer damage, such asscratching, delamination, or destruction of material layers on thewafer. When the wafer is fragile, as is generally the case withsubstrates layered with films such as porous films having a lowdielectric constant, these damage issues are particularly acute anddetrimental in terms of wafer yield and performance. Generally, fasterchemical-mechanical polishing results in more defects.

Additional approaches have involved using various protected combinationsof oxidizers, chelators, corrosion inhibitors, solvents, and otherchemicals in the slurry, various abrasives including for example azirconium abrasive or mixed abrasives, and/or using point-of-use mixingtechniques. These approaches are generally undesirable, as theytypically complicate CMP in terms of tooling and process control forexample, consume more process time, and/or increase costs.

Chelators act on the metal surface of the substrate to turn metal oxideswater soluble. Examples of chelators include a wide range of organicacids, such as salicylic acid, see e.g. U.S. patent application Ser.Nos. 09/795,421;. 09/859,147; 10/393,074 & 10/246,280. Other approacheshave included the use of phosphoric acid as well as organic acids. U.S.patent application Ser. No. 10/396,410. Chelators may be used inconjunction with oxidizers. When an oxidizer and chelator are used incombination, excessive corrosion of the substrate may result. As asolution to this problem, corrosion inhibitors may be added to thecomposition. For the typical CMP substrate—copper—examples of corrosioninhibitors include imidazole or benzothiazole. Addition of suchcorrosion inhibitors can be cumbersome often requiring a specializedmethod. See e.g. JP-A-11-21546. Furthermore, the chemistry of CMPcompositions may limit the group of suitable corrosion inhibitors.

U.S. Pat. No. 5,417,877 describes organic stripping compositions for usein stripping polymeric material, where the composition comprises polarorganic solvents, basic amines, and inhibitors, wherein the broad classof inhibitors described includes salicylic acid compounds.

U.S. Patent Publication No. 2003/0130147 describes stripping and residueremoving compositions having 1) glycol ethers, alcohols having a cyclicalkoxy group, alcohols having a heterocyclic oxy group containingnitrogen or sulfur as the hetero atom, or alcohols having a cyclic etherstructure containing at least oxygen as the hetero atom; and 2)anticorrosives selected from aromatic hydroxyl compounds, acetylenicalcohol, carboxyl-group-containing organic compounds such as quinaldinicacid, triazole-based compounds, and/or purine-based compounds, and mayoptionally contain any of water, an organic acid of which salycilic acidis an example, and amines.

U.S. Patent Publication No. 2002/0019202 describes a two-step CMP methodfor semi-conductors with composition that can include complexing agentssuch as salicylic acid, 3-hydroxy-salicylic acid, or3,5-hydroxy-salicylic acid, inter alia, but preferably citric acid, andcorrosion inhibitors such as substituted or unsubstitutedbenzotriazoles, preferably benzotriazole.

U.S. Patent Publication Nos. 2001/0024933 and 2003/0181046 describe aCMP composition and method that contains an oxidizing agent, an organicpolymer removal rate suppressant, and optionally a complexing agent,which can include salicylic acid, 3-hydroxy-salicylic acid, or3,5-hydroxy-salicylic acid, ethylenediamine, and ethyl acetoacetate,inter alia.

U.S. Patent Publication Nos. 2002/0016073 and 2003/0186497 describecompositions and methods for polishing semiconductors containing anoxidizer, phosphoric acid, organic acid, a corrosion inhibition, andwater. While salicylic acid is listed as one of the organic acids inthese publications, it is not a preferred acid, nor is it mentioned as acorrosion inhibitor.

U.S. Patent Publication No. 2003/0041526 describes a polishingcomposition having an index of degree of sedimentation from 80 to 100and which can contain an abrasive, water, and optionally a 2-20 carbonatom hydroxy-functional or mercapto-functional carboxylic acid. Whilesalicylic acid is listed as one of the functional carboxylic acids inthis publication, it is not a preferred acid.

U.S. Patent Publication No. 2002/0017630 discloses a liquid abrasivecomposition containing (1) an oxidizing agent for a metal, (2) adissolving agent for an oxidized metal, (3) a first protectingfilm-forming agent such as an amino acid or an azole which adsorbsphysically on the surface of the metal and/or forms a chemical bond, tothereby form a protecting film, (4) a second protecting film-formingagent such as polyacrylic acid, polyamido acid or a salt thereof whichassists the first protecting film-forming agent informing a protectingfilm and (5) water. While salicylic acid is listed as one of thedissolving agents in this publication, it is not disclosed as being apreferred organic acid for this purpose.

U.S. Patent Publication No. 2001/0014534 stripper compositioncontaining: an anticorrosive agent containing (a) urea or a ureaderivative and (b) a hydroxy aromatic compound; optionally (c) ahydroxylamine or an alkanolamine; and optionally (d) water. Whilesalicylic acid is listed as one of the hydroxy aromatic compounds inthis publication, it is not a preferred element of the anticorrosiveagent.

U.S. Patent Publication No. 2003/0181345 describes a CMP solution forremoving tantalum barrier materials that contains up to 25 wt % of anoxidizer, up to 15 wt % of an inhibitor for a nonferrous metal, up to 20wt % of a complexing agent for the nonferrous metal, 0.01 to 12 wt % ofa tantalum removal agent, up to 5 wt % of an abrasive, up to 15 wt ofpolymeric or polymer-coated particles, and the balance water. Whilesalicylic acid, 3-hydroxysalicylic acid, and 3,5-dihydroxysalicylic acidare listed as examples of complexing agents in this publication, noneare preferred complexing agents, nor are any mentioned as non-ferrousmetal corrosion inhibitors.

U.S. Patent Publication No. 2002/0169088 describes a cleaningcomposition comprises a carboxylic acid, an amine-containing compound, aphosphonic acid, and water. While salicylic acid (a monocarboxylic acid)is listed as one of the carboxylic acids in this publication, thepublication teaches that preferred acids contain at least two carboxylicacid groups, with three carboxylic acid groups being even morepreferred.

U.S. Patent Publication No. 2002/0034925 discloses a semiconductorpolishing process using a slurry composition comprising abrasivesdispersed in an a medium. According to the publication, the abrasive canbe made of organic matter, which may include, inter alia,acetylsalicylic acid and salts of salicylic acids.

U.S. Patent Publication No. 2003/0171239 discloses methods andcompositions for treating a surface of a substrate by foam technologyusing a liquid composition containing a gas; a surfactant; and at leastone component selected from the group consisting of a fluoride, ahydroxylamine, an amine, and periodic acid.

U.S. Patent Publication No. 2003/0137052 discloses a method forsemi-conductor manufacturing that includes: a CMP step using acomposition containing quinaldinic acid, lactic acid, colloidal silica,hydrogen peroxide, and optionally benzotriazole, followed by anoxygen-rich water polish; a post-CMP cleaning step using at least one ofan organic acid (that can include, inter alia, salicylic acid), aninorganic acid, and an alkali, optionally a surface-active agent, andoptionally a separate chelating agent such as EDTA; and a rinsing stepusing an oxygen-rich aqueous solution.

U.S. Patent Publication No. 2003/0130147 discloses a strippingcomposition containing a hydroxy-functional ether compound, ananticorrosive agent, and optionally a weak organic or inorganic acid.While salicylic acid is listed as one of the weak organic acids in thispublication, it is not a preferred optional acid component.

Another approach has involved increasing the amount of oxidizing agentused in the CMP slurry in an effort to increase chemical removal oftargeted material. This approach is largely disfavored as the use ofincreased amounts of oxidizing agents increase material costs and alsodetrimentally add to the handling issues and environmental issuesassociated with many oxidizing agents and also increase costs.

It is generally known that oxidizers admixed in a solution can providesynergistic etching rates. While ferric salts, cerium salts, peroxides,persulfates, or hydroxylamines form the oxidizing capacity of mostcommercially available CMP slurries, those of ordinary skill in the arthave long known that these oxidizers can be admixed with others in thisgroup and also with other oxidizers, and the resulting composition canshow synergistic results.

Certain metals, such as those with a tendency to plate on or be absorbedon to at least one part of the substrate, are more damaging than othermetals. The industry has developed methods to remove a portion of themetallic contamination, for example by: physical desorption by solvents;changing the surface charge with either acids or bases so that Si——OH orM——OH group can be protonated (made positive) in acid or made negativewith bases by removing the proton; ion competition, for example removingadsorbed metal ions by adding acid (i.e. ion exchange); subsequentoxidation of metals to change the chemical bonds between the impuritiesand substrate surface; and subsequent etching the surface, wherein theimpurity and a certain thickness of the substrate surface is removed, asdescribed in U.S. Pat. No. 6,313,039, the contents of which has beenincorporated herein by reference. This patent taught the synergistic useof combinations of oxidizers, partticularlynon-transition-metal-containing oxidizers, including a ammoniumpersulfate/peroxymonosulfate system; a hydroxylaminenitrate/hydroxylamine system; an ammonium persulfate/periodic acidsystem (for example at 0.5% to 2% periodic acid concentrations; ahydrogen peroxide/hydroxylamine system; an ammonium persulfate/potassiumperiodate system; and an ammonium persulfate/potassium iodate system.There have been various “post-polishing cleaners” developed to removemetallic contamination, but removal of all undesired metal ions issubstantially beyond the range of cleaners, and as the size of thestructures continues to decrease, even a very small number of metallicatoms deposited on a surface will result in undesired shorts or currentleakage.

Therefore, despite the known advantages of having multiple oxidizers,for example a metal-containing oxidizer admixed with either anothermetal-containing oxidizer or with a non-metal-containing oxidizer, therehas been a tendency in the industry to reduce the amount of metal ionsin CMP slurries. Additionally, metal ion-containing fluids are oftenenvironmentally undesirable and expensive treatment may be needed priorto waste disposal of used product.

Chemical-mechanical planarization (CMP) and post-CMP cleaning havebecome key steps in the fabrication of high-speed integrated circuits.The oxidant in CMP slurries plays a critical role in controlling theremoval rate and planarity of metal films that are polished. Recently,hydroxylamine-(NH2OH—) based oxidants have been introduced for chemicalmechanical polishing of copper. See, e.g., International Publication No.WO 98/04646 and M. L. Peterson et al., Semiconductor Fabtech, 11th ed.(2000), the entire contents of which are hereby incorporated byreference for all purposes. The etch rate and CMP removal rate of copperin. hydroxylamine based solutions is a strong function of pH andexhibits a maximum in the vicinity of pH 6. See, e.g., W. Huang et al.,Chemical Mechanical Planarization in IC DEVICE MANUFACTURING III, PV99-37, p. 101, The Electrochemical Society Proceedings Series,Pennington, N.J. (1999). The removal rates at pH 6 can be modulatedthrough the use of a corrosion inhibitor such as benzotriazole (BTA).While BTA has been known to be a very good corrosion inhibitor forcopper for many decades, due to certain environmental limitationsimposed by this compound, the CMP industry has been looking foralternatives to BTA.

EKC Technology/Dupont Electronic Technologies, a large commercialmanufacturer of CMP slurries, sells several high-purity, non-metal-basedCMP slurries for tungsten, for example the MicroPlanar® CMP3550™/MicroPlanar® CMP3510™ slurry, as well as the traditional but effectiveferric nitrate as the oxidizer with a post-CMP cleaner to remove metalcontaminants.

Further developments in the field of CMP technology are desired.Alternative corrosion inhibitor additives for use in metal freeoxidizer-based, for example hydrogen peroxide-based, CMPsolutions/slurries are addressed herein.

SUMMARY OF THE INVENTION

The invention provides a method for chemically polishing mechanicallypolishing a metal-containing substrate comprising contacting ametal-containing substrate with a composition comprising: an oxidizingagent; between about 0.0001 M to about 1 M of a salicylic acid compound,wherein the salicylic acid compound is present in an amount sufficientto substantially inhibit corrosion and water, at a temperature and for atime sufficient to chemically mechanically polish the metal-containingsubstrate.

The invention further provides a method of cleaning a metal-containingsubstrate that had previously undergone a chemical mechanical polishingprocess comprising the steps of contacting the chemically mechanicallypolished metal-containing substrate with a composition comprising: anoxidizer; a salicylic acid compound and water, at a temperature and fora time sufficient to clean the metal-containing substrate.

The invention further provides a method of a post-etch residue removalfor a metal-containing substrate comprising the steps of contacting thechemically mechanically polished metal-containing substrate with acomposition comprising of: an oxidizer; a salicylic acid compound; andwater at a at a temperature and for a time sufficient to removepost-etch residue from the metal-containing substrate.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Benzotriazole (BTA) is a well-known corrosion inhibitor for copper invarious applications in a wide-range of environments. The chemistry ofinteraction of benzotriazole (BTA) with copper has been studiedextensively. See, e.g., G. W. Poling, Corros. Sci., (1970), 10, p.359,and V. Brusic et al., Electrochem. Soc., (1991), 138, p.2253. It isgenerally accepted that BTA (as well as BTA-ion) chemisorbs on thecopper surface and forms an insoluble cuprous surface complex. Undercertain conditions the formation of a thick, multilayered coating hasbeen confirmed. See, e.g., V. Brusic et al., Electrochem. Soc., (1991),138, p.2253.

One aspect of the present invention includes a composition, e.g., usedin a method for chemical mechanical polishing of a metal-containingsubstrate, particularly of copper-containing substrates, containing:between about 0.01% and about 30% by weight of an oxidizing agent basedon weight of fluid; between about 0.00001M to about 0.5M, preferablyfrom about 0.00005M to about 0.05M, for example from about 0.00005M toabout 0.001M, from about 0.0001M to about 0.01M, from about 0.0001M toabout 0.001M, from about 0.001M to about 0.01M, or from about 0.01M toabout 0.5M of salicylic acid or a salicylic acid derivative; water; andoptionally an abrasive.

Generally, any quantity of salicylic acid and/or its derivative(s),particularly salicylic acid, can act as a chelator while there cantypically be a certain minimum quantity before the salicylic acid and/orits derivative(s), for example salicylic acid, can become effective as acorrosion inhibitor.

Generally, a quantity greater than about 0.005M, preferably greater thanabout 0.01M, of salicylic acid will function as a corrosion inhibitor.When used in a CMP step on a copper-containing substrate, for example,the amount of salicylic acid and/or its derivative(s) present canadvantageously be at least sufficient to chelate at least about 50% ofthe copper chemically and/or mechanically polished from the substrateduring the CMP process, for example such that not more than about 300ppm of unchelated copper ions are present in the CMP solution/slurry,more preferably at least about 75% of the available copper ions insolution and/or such that not more than about 100 ppm, or not more thanabout 50 ppm of unchelated copper ions are present in the CMPsolution/slurry. When used for example in shallow trench isolation (STI)processes, it is advantageous to have sufficient salicylic acid and/orits derivative compounds available to act as a corrosion inhibitor.

When used in a post-CMP cleaning step of a copper-containing substrate,the fluid advantageously contains an oxidizer, and includes an amount ofsalicylic acid and/or its derivative(s) also advantageously sufficientto at least partially inhibit corrosion of at least a portion of thecopper-containing substrate (or of a copper-containing layer of amulti-layer substrate) during the cleaning process, preferably tosubstantially inhibit corrosion of the copper-containing portion(s) ofthe substrate. As used herein, the term “substantially” should beunderstood to refer to a level of at least about 30%, preferably a levelof at least about 70%, more preferably a level of at least about 90%,for example a level of at least about 95% compared to the corrosionobserved using a solution without the salicylic acid compound. In apreferred embodiment, the term “substantially” can mean completely.Generally, any quantity of salicylic acid and/or its derivative(s),particularly salicylic acid, can act as a chelator while there cantypically be a certain minimum quantity before the salicylic acid and/orits derivative(s), particularly salicylic acid, can become effective asa corrosion inhibitor. The amount of salicylic acid and/or itsderivative(s) can be from about 0.00001M to about 1 M, for example fromabout 0.05M to about 0.2M, alternatively from about 0.00005M to about0.001M, from about 0.001M to about 0.01M, alternatively from about 0.01Mto about 0.1M, alternatively from about 0.1M to about 0.5M. A quantitygreater than about 0.005M, preferably greater than about 0.01M, ofsalicylic acid will be most useful as a corrosion inhibitor.

The composition according to the invention can be used on ametal-containing substrate, preferably a copper-containing substrateand/or a tantalum-containing substrate (e.g., copper, copper alloys suchas Cu—Al, tantalum, tantalum nitrides, tantalum oxynitrides, tantalumoxides, tantalum alloys, and the like, and combinations thereof). Thecomposition can contain an oxidizing agent, preferably an organic orinorganic peroxide such as hydrogen peroxide, a corrosion inhibitorsubstitute for benzotriazole, preferably a salicylic acid and/or aderivative thereof such as salicylic acid, water, and optionally anabrasive. When used as a CMP slurry, it is preferred that thecomposition contain an abrasive. However, it is envisioned that the CMPcomposition may be used in conjunction with an abrasive polishing pad(e.g., a polishing pad having abrasive particles attached thereto orcontained therein), in which case the abrasive in the slurry may beunnecessary and therefore optional. When used in a post-CMP cleaner,generally the abrasive is not desired.

The present invention can be used in conjunction with any suitablesubstrate. In particular, the present invention can be used inconjunction with memory or rigid disks, metals (e.g., noble metals), ILDlayers, integrated circuits, semiconductor devices, semiconductorwafers, micro-electro-mechanical systems, ferroelectrics, magneticheads, polymeric films, and low and high dielectric constant films, andtechnical or optical glass. Suitable substrates comprise, for example, ametal, metal oxide, metal composite, or mixtures thereof. The substratecan comprise, consist essentially of, or consist of any suitable metal.Suitable metals include, for example, copper, aluminum, titanium,tungsten, tantalum, gold, platinum, iridium, ruthenium, and combinations(e.g., alloys or mixtures) thereof. The substrate also can comprise,consist essentially of, or consist of any suitable metal oxide. Suitablemetal oxides include, for example, alumina, silica, titania, ceria,zirconia, germania, magnesia, and coformed products thereof, andmixtures thereof. In addition, the substrate can comprise, consistessentially of, or consist of any suitable metal composite and/or metalalloy. Suitable metal composites and metal alloys include, for example,metal nitrides (e.g., tantalum nitride, titanium nitride, and tungstennitride), metal carbides (e.g., silicon carbide and tungsten carbide),nickel-phosphorus, alumino-borosilicate, borosilicate glass,phosphosilicate glass (PSG), borophosphosilicate glass (BPSG)),silicon/germanium alloys, and silicon/germanium/carbon alloys. Thesubstrate also can comprise, consist essentially of, or consist of anysuitable semiconductor base material. Suitable semiconductor basematerials include single-crystal silicon, poly-crystalline silicon,amorphous silicon, silicon-on-insulator, and gallium arsenide. Glasssubstrates can also be used in conjunction with the present inventionincluding technical glass, optical glass, and ceramics, of various typesknown in the art.

The formulations are particularly useful on substrates comprising,consisting essentially of, or consisting of copper, a copper alloy,and/or a copper compound, and the substrate may also contain one or morebarrier materials as are known in the art, such as Ta, TaN, Ti, TiN, orcombinations thereof

The present invention can be used to polish any part of a substrate(e.g., a semiconductor device) at any stage in the production of thesubstrate. For example, the present invention can be used to polish asemiconductor device in conjunction with shallow trench isolation (STI)processing, as set forth, for example, in U.S. Pat. Nos. 5,498,565;5,721,173; 5,938,505; and 6,019,806, or in conjunction with theformation of an interlayer dielectric.

The present invention, incorporated into a chemical mechanical polishingcomposition, a post-etch residue remover, or a post-CMP cleaner, can beused in conjunction with any suitable component (or ingredient) known inthe art for each category, for example, abrasives, oxidizing agents,catalysts, film-forming agents, complexing agents, Theological controlagents, surfactants (i.e., surface-active agents), polymericstabilizers, pH-adjusters, and other appropriate ingredients.

The abrasive, when present in the compositions according to theembodiments used for chemical mechanical polishing, can be any suitableabrasive known in the CMP art. For example, suitable abrasives caninclude, but are not limited to, silica, ceria, alumina, zirconia,titania, metal coated particles thereof (e.g., iron-coated silica),magnesia, co-formed products thereof, mixtures thereof, and chemicaladmixtures thereof. The term “chemical admixture” refers to particlesincluding atomically mixed or coated metal oxide abrasive mixtures.Suitable abrasives also include heat-treated abrasives andchemically-treated abrasives (e.g., abrasives with chemically-linkedorganic functional groups).

The amount of abrasive, when present in the compositions according tothe invention, can advantageously be from about 0.01% to about 30% byweight, preferably from about 0.01% to about 10%, for example from about0.01% to about 5% or from about 0.1% to about 10%. In some embodimentsaccording to the invention, the composition can be substantially free ofabrasives.

The abrasive can be produced by any suitable technique known to one ofordinary skill in the art. The abrasive can be derived, for example,from any process known in the art, including flame processes, sol-gelprocesses, hydrothermal processes, plasma processes, aerogel processes,fuming processes, precipitation processes, mining, and combinations ofprocesses thereof. The abrasive can be a condensation-polymerized metaloxide, e.g., condensation-polymerized silica. A suitable abrasive alsocan comprise, consist essentially of, or consist of high-temperaturecrystalline phases of alumina consisting of gamma, theta, delta, andalpha alumina, and/or low-temperature phases of alumina consisting ofall non-high temperature crystalline alumina phases.

The abrasive can be combined with any suitable carrier (e.g., an aqueouscarrier) to form a “dispersion” (e.g., a “slurry”). Suitable dispersionscan have any suitable concentration of abrasive.

The abrasive can have any suitable abrasive particle characteristicsdepending on the desired polishing effects. In particular, the abrasivecan have any suitable surface area. A suitable abrasive surface area,for example, is a surface area ranging from about 5 m²/g to about 430m²/g, as calculated from the method of S. Brunauer, P. H. Emrnet, and I.Teller, J. Am. Chemical Society, 60, 309 (1938). Alternatively, it isalso suitable for the abrasive to have essentially a bimodal particlesize distribution.

Any suitable oxidizing agent can be used in conjunction with the presentinvention. Suitable oxidizing agents include, for example, oxidizedhalides (e.g., chlorates, bromates, iodates, perchlorates, perbromates,periodates, fluoride-containing compounds, and mixtures thereof, and thelike). Suitable oxidizing agents also include, for example, perboricacid, periodic acid, periodates, perborates, percarbonates, nitrates(e.g., iron (III) nitrate, and hydroxylamine nitrate), persulfates(e.g., ammonium persulfate), organic peroxides such as benzoyl peroxide,inorganic peroxides such as hydrogen peroxide, peroxyacids (e.g.,peracetic acid, perbenzoic acid, m-chloroperbenzoic acid, salts thereof,mixtures thereof, and the like), permanganates, chromates, ceriumcompounds, ferricyanides (e.g., potassium ferricyanide), mixturesthereof, and the like. Suitable oxidizers also include hydroxylamine,hydroxylamine derivatives, and/or salts thereof Examples of suitablehydroxylamine or hydroxylamine derivative include hydroxylamine,N-methyl-hydroxylamine, N,N-dimethyl-hydroxylamine,N-ethyl-hydroxylamine, N,N-diethyl-hydroxylamine, hydroxylamine nitrate,hydroxylamine sulfate, hydroxylamine phosphate. Suitable oxidizers canoften be mixtures of two or more of the above-listed oxidizers, in arange of from about 100:1 to about 1:100. The amount of suitableoxidizing agent or agents can be between about 0.01% to about 30%, e.g.,between 0.01% and about 2%, alternatively between about 2% and about 5%,alternatively between about 5% and about 10%, alternatively betweenabout 10% and about 17.5%, alternatively between about 17.5% and about25%, alternatively between about 25% and about 30%.

Any suitable film-forming agent (i.e., corrosion-inhibitor) can be usedin conjunction with the present invention, supplementing thefilm-forming capacity of the salicylic acid and/or its derivative(s).Suitable film-forming agents include, for example, heterocyclic organiccompounds (e.g., organic compounds with one or more active functionalgroups, such as heterocyclic rings, particularly nitrogen-containingheterocyclic rings). Suitable film-forming agents also include, forexample, benzotriazole, triazole, benzimidazole, and mixtures thereof.In one embodiment, the film-forming agent can be present in an amountfrom about 0.05% to about 10% (exclusive of the salicylic acid and/orits derivative compounds according to this invention) by weight based onthe weight of the fluid.

Any suitable complexing agent (i.e., chelating agent or selectivityenhancer) can be used in conjunction with the present invention,supplementing the chelating capacity of the salicylic acid and/or itsderivative(s). Suitable complexing agents include, for example, carbonylcompounds (e.g., acetylacetonates and the like), simple carboxylates(e.g., acetates, aryl carboxylates, and the like), carboxylatescontaining one or more hydroxyl groups (e.g., glycolates, lactates,gluconates, gallic acid and salts thereof, and the like), di-, tri-, andpoly-carboxylates (e.g., oxalates, phthalates, citrates, succinates,tartrates, maleates, glycolates, edetates such as disodium EDTA,mixtures thereof, and the like), carboxylates containing one or moresulfonic and/or phosphonic groups, and carboxylates, di-, tri-, orpoly-alcohols (e.g., ethylene glycol, pyrocatechol, pyrogallol, tannicacid, and the like), phosphate-containing compounds (e.g., phosphoniumsalts, phosphonic acids, and the like), amine-containing compounds(e.g., amino acids, amino alcohols, di-, tri-, and poly-amines, and thelike), or mixtures thereof. In one embodiment, a complexing agent can bepresent in an amount from about 0.005% to about 5% by weight (exclusiveof the salicylic acid and/or its derivative compounds according to thisinvention) based on the weight of the fluid.

Any suitable surfactant and/or rheological control agent can be used inconjunction with the present invention, including viscosity enhancingagents and coagulants. Suitable rheological control agents include, forexample, polymeric rheological control agents. Moreover, suitablerheological control agents include, for example, urethane polymers(e.g., urethane polymers with a molecular weight greater than about100,000 Daltons), acrylates comprising one or more acrylic subunits(e.g., vinyl acrylates and styrene acrylates), polymers, copolymers, andoligomers thereof, and salts thereof. Suitable surfactants include, forexample, cationic surfactants, anionic surfactants, anionicpolyelectrolytes, nonionic surfactants, amphoteric surfactants,fluorinated surfactants, mixtures thereof, and the like. In oneembodiment, the surfactant and/or rheological control agent can bepresent in an amount from about 0.005% to about 4% by weight based onthe weight of the fluid.

The composition used in conjunction with the present invention cancontain any suitable polymeric stabilizer or other surface activedispersing agent, for example, phosphoric acid, organic acids, tinoxides, organic phosphonates, and the like, and mixtures thereof. In oneembodiment, the polymeric stabilizer can be present in an amount fromabout 0.01% to about 3% by weight based on the weight of the fluid.

Any of the components used in conjunction with the present invention canbe provided in the form of a mixture or solution in an appropriatecarrier liquid or solvent (e.g., water or an appropriate organicsolvent).

Furthermore, as mentioned, the compounds, alone or in any combination,can be used as a component of a polishing, residue removing or cleaningcomposition. Two or more components then are individually stored andsubsequently mixed to form a polishing or cleaning composition at, orimmediately before reaching, the point-of-use.

A component can have any pH appropriate in view of the storage andcontemplated end-use, as will be appreciated by those of skill in theart. Moreover, the pH of a component used in conjunction with thepresent invention can be adjusted in any suitable manner, e.g., byadding a pH adjuster, regulator, or buffer. Suitable pH adjusters,regulators, or buffers include acids, such as, for example, hydrochloricacid, acids such as mineral acids (e.g., nitric acid, sulfuric acid,phosphoric acid, and the like), and organic acids (e.g., acetic acid,citric acid, malonic acid, succinic acid, tartaric acid, oxalic acid,glycolic acid, and the like). Suitable pH adjusters, regulators, orbuffers also include bases, such as, for example, inorganic hydroxidebases (e.g., sodium hydroxide, potassium hydroxide, ammonium hydroxide,and the like) and carbonate bases (e.g., sodium carbonate and the like).In one preferred embodiment, the composition contains an organic acidsuch as acetic acid.

As described above, various embodiments of the invention can containother additives, including, but not limited to, polar organic solvents,non-polar organic solvents, surfactants, chelating agents and/orcorrosion inhibitors other than salicylic acids and their derivatives,non-hydroxyl-containing amines, other hydroxyl-containing amines such asalkanolamines, organic and/or inorganic acids and/or bases (e.g., tocontrol pH), oxidizing agents other than hydroxylamine or itsderivatives, ammonium salts, mono-, di-, tri-, and/or tetra-alkylammonium salts, or the like, or a combination thereof. In apreferred embodiment, the above described compositions can also besubstantially free from one or more of the following: polar organicsolvents; non-polar organic solvents; surfactants; chelating agentsand/or corrosion inhibitors other than salicylic acids and theirderivatives; non-hydroxyl-containing amines; other hydroxyl-containingamines such as alkanolamines; organic and/or inorganic acids and/orbases (e.g., to control pH); oxidizing agents other than organic orinorganic peroxides such as hydrogen peroxide; ammonium salts; andmono-, di-, tri-, and/or tetra- alkylammonium salts.

The polishing and cleaning components described herein can be combinedin any manner and proportion to provide one or more compositionssuitable for polishing or cleaning a substrate (e.g., a semiconductorsubstrate).

Another aspect of the present invention includes a composition, e.g.,used for chemical mechanical polishing or post-CMP cleaning,particularly of copper-containing substrates, containing an organic orinorganic peroxide such as hydrogen peroxide, salicylic acid and/or itsderivative(s), particularly salicylic acid, water, an organic acid suchas acetic acid, and optionally an abrasive such as silica. When used ina CMP step on a copper-containing substrate, the amount of salicylicacid and/or its derivative(s) present is advantageously sufficient tochelate a portion of the copper chemically and/or mechanically polishedfrom the substrate during the CMP process, preferably at least about 50%of the available copper ions in solution and/or such that not more thanabout 100 ppm of unchelated copper ions are present in the CMPsolution/slurry, more preferably at least about 75% of the availablecopper ions in solution and/or such that not more than about 50 ppm ofunchelated copper ions are present in the CMP solution/slurry. When usedin a post-CMP cleaning step of a copper-containing substrate, the amountof salicylic acid and/or its derivative(s), particularly salicylic acid,present is advantageously sufficient to inhibit corrosion of at least aportion of the copper-containing substrate (or of a copper-containinglayer of a multi-layer substrate) during the cleaning process,preferably to substantially inhibit corrosion of the copper-containingportion(s) of the substrate. As used herein, the term “substantiallyinhibit” should be understood to refer to inhibiting static corrosion toa level of at least about 30%, preferably a level of at least about 70%,more preferably a level of at least about 90%, for example a level of atleast about 95% less than is observed with a similar composition notcontaining the salicylic acid. In a preferred embodiment, the term“substantially” can mean completely.

Advantageously, the composition according to the invention can be anaqueous solution containing salicylic acid and/or its derivative(s), andan organic or inorganic peroxide such as hydrogen peroxide, or anaqueous slurry containing salicylic acid and/or its derivative(s), anorganic or inorganic peroxide such as hydrogen peroxide, and anabrasive. In one embodiment, the composition consists essentially ofwater, acetic acid, salicylic acid, and hydrogen peroxide. In anotherembodiment, the composition consists essentially of water, acetic acid,salicylic acid, hydrogen peroxide, and an abrasive such as silica.

The amount of organic and/or inorganic peroxide in the compositionsaccording to the invention can advantageously be from about 0.01M toabout 3M, preferably from about 0.01M to about 1M, for example fromabout 0.05M to about 0.5M. As used herein, the designation “M” refers tomolarity, which is typically expressed in moles per liter ofcomposition. In an alternate embodiment, the amount of organic and/orinorganic peroxide in the compositions according to the invention canadvantageously be from about 0.01% to about 25% by weight, preferablyfrom about 0.03% to about 15% by weight, for example from about 0.03% toabout 0.5% by weight, from about 0.1% to about 1% by weight, from about1% to about 15% by weight, from about 0.1% to about 5% by weight, fromabout 0.5% to about 5% by weight, from about 0.03% to about 1% byweight, or from about 10% to about 15% by weight.

Salicylic acid compound derivatives are compounds having the generalformula:

where R¹ and R₂ can independently be hydrogen; an organicsalt/counterion such as ammonium, a mono-, di-, tri-, or tetra- C₁-C₈alkyl ammonium, or the like; an inorganic salt/counterion such assodium, potassium, lithium, a phosphonium, or the like; a C₁-C₂₀ linearor branched, saturated or unsaturated, optionally singly or multiplysubstituted alkyl moiety; a C₅-C₂₀ optionally singly or multiplysubstituted aryl or heteroaryl moiety; or a combination thereof, andwhere R₃ is a hydrogen, a C₁-C₂₀ linear or branched, saturated orunsaturated, optionally singly or multiply substituted alkyl moiety, aC₅-C₂₀ optionally singly or multiply substituted aryl or heteroarylmoiety, or a combination thereof. Optionally substituted moieties caninclude, but are not limited to hydroxyls, nitro groups, sulfates,phosphates, amines, amides, carboxylic acids, carboxylate salts,carboxylate esters, halides, alkyl or aryl ethers, C₁-C₆ linear orbranched, saturated or unsaturated alkyl groups, C₅-C₁₂ aryl groups, orthe like, or a combination or reaction product thereof. In one preferredembodiment, R₁, R₂, and R₃ are all hydrogen (i.e., which results insalicylic acid). In another preferred embodiment, R₂ and R₃ are bothhydrogen and R₁ is a an inorganic salt/counterion.

Salicylic acid compounds according to the invention can additionally oralternately include complexes of salicylic acid (i.e., R₁, R₂, and R₃are all hydrogen, as above) with other molecules, e.g., triethanolamine.In addition, another salicylic acid compound according to the inventionis salicylic hydrazide, where the —OR₁ moiety in the structure above isreplaced by an —NH—NH₂ moiety.

The amount of salicylic acid and/or its derivative(s) in the polishing,residue removing and post-CMP cleaning compositions according to theinvention can advantageously be from about 0.00001M to about 1M,preferably from about 0.00005M to about 0.5M, for example from about0.00005M to about 0.001M, from about 0.001M to about 0.01M, from about0.01M to about 0.1M, or from about 0.1M to about 0.5M. In an alternateembodiment, the amount of salicylic acid and/or its derivative(s) in thecompositions according to the invention can advantageously be from about0.01% to about 25% by weight, preferably from about 0.03% to about 15%by weight, for example from about 0.03% to about 0.5% by weight, fromabout 0.1% to about 1% by weight, from about 1% to about 15% by weight,from about 0.1% to about 5% by weight, from about 0.5% to about 5% byweight, from about 0.03% to about 1% by weight, or from about 10% toabout 15% by weight. Generally, any quantity of salicylic acid and/orits derivative(s), particularly salicylic acid, can act as a chelatorwhile there is typically a certain minimum quantity before the salicylicacid and/or its derivative(s), particularly salicylic acid, can becomeeffective as a corrosion inhibitor. The quantity useful for inhibitingcorrosion on a particular substrate with a particular quantity ofoxidizer will be readily ascertainable by one of ordinary skill in theart having the benefit of this disclosure.

One particular embodiment comprises adding glacial salicylic acid(aspirin) to a CMP composition, residue removing composition, and orpost-CMP cleaning composition in an amount sufficient to chelate metalswithin the composition and preferably, in an amount sufficient tosubstantially inhibit corrosion of metal, e.g., copper, on thesubstrate. A chelating amount may be from about 0.01% to about 2%,typically about 0.01% to about 1%. Corrosion inhibiting amounts aretypically from about 4% to about 10%. Intermediate values have bothfunctions.

Aspects of the invention relating to a method for chemicallymechanically planarizing-or polishing a metal-containing substrate,comprise contacting a copper-containing substrate with a compositionaccording to the invention for a time and at a temperature sufficient toplanarize, and polish copper-containing surface thereof. In a preferredembodiment, compositions useful for this method can include an abrasivesuch as silica.

Another aspect of the invention relates to a method for cleaning apreviously chemically-mechanically planarized or polishedcopper-containing substrate that includes contacting the polishedsubstrate with a composition according to the invention for a time andat a temperature sufficient to planarize, polish, or clean acopper-containing surface thereof. In a preferred embodiment,compositions useful for this method can be substantially free of anabrasive.

The method of CMP includes contacting the fluid or slurry comprising theoxidizer and salicylic acid and/or its derivative(s) with the substrateunder movable conditions, where the fluid or slurry is typically betweenthe substrate and a pad that move relative to one another, to polishsubstrate material.

Any suitable polishing pad can be used in conjunction with the presentinvention. In particular, the polishing pad can be woven or non-wovenand can comprise any suitable polymer of varying density, hardness,thickness, compressibility, ability to rebound upon compression, andcompression modulus. The polishing pad used in conjunction with thepresent invention preferably has a density of about 0.6 to about 0.95g/cm³, a Shore A hardness rating of less than about 100 (e.g., about 40to about 90), a thickness of at least about 0.75 mm (e.g., about 0.75 toabout 3 mm), compressibility of about 0 to about 10% (by volume), theability to rebound to at least about 25% (by volume) (e.g., about 25% toabout 100%) after compression at about 35 kPa, and a compression modulusof at least about 1000 kPa. Examples of suitable polymers includepolyurethanes, polymelamines, polyethylenes, polyesters, polysulfones,polyvinyl acetates, polyacrylic acids, polyacrylamides,polyvinylchlorides, polyvinylfluorides, polycarbonates, polyamides,polyethers, polystyrenes, polypropylenes, nylons, fluorinatedhydrocarbons, and the like, and mixtures, copolymers, and graftsthereof. Preferably, the polishing pad comprises a polyurethanepolishing surface. The polishing pad and/or surface can be formed fromsuch materials using suitable techniques recognized in the art, forexample, using thermal sintering techniques. Furthermore, the polishingpad formed from such materials can be substantially porous (e.g., havingopen or closed pores) or substantially non-porous. Porous padspreferably have a pore diameter of about 1 to about 1000 microns and apore volume of about 15% to about 70%. The polishing pad and/or surfacealso can be perforated or unperforated to any degree. Preferably, thepolishing pad comprises a perforated polishing surface.

The method of post clean treatment involves contacting the substrate,after the CMP process, with the post CMP cleaner under conditions toremove the CMP slurry.

1-19. (canceled)
 20. A method of cleaning a metal-containing substratethat had previously undergone a chemical mechanical polishing processcomprising the steps of: contacting the chemically mechanically polishedmetal-containing substrate with a composition comprising: an oxidizer; asalicylic acid compound having the formula:

where R₁ and R₂ are independently hydrogen, an organic salt/counterion,an inorganic salt/counterion, a C₁-C₂₀ linear or branched, saturated orunsaturated, optionally singly or multiply substituted alkyl moiety, aC₅-C₂₀ optionally singly or multiply substituted aryl or heteroarylmoiety, or a combination thereof, and where R₃ is a hydrogen, a C₁-C₂₀linear or branched, saturated or unsaturated, optionally singly ormultiply substituted alkyl moiety, a C₅-C₂₀ optionally singly ormultiply substituted aryl or heteroaryl moiety, or a combinationthereof, and wherein optionally substituted moieties comprise hydroxyls,nitro groups, sulfates, phosphates, amines, amides, carboxylic acids,carboxylate salts, carboxylate esters, halides, alkyl or aryl ethers,C₁-C₆ linear or branched, saturated or unsaturated alkyl groups, C₅-C₁₂aryl groups, or the like, or a combination or reaction product thereof;and water, wherein the contacting occurs at a temperature and for a timesufficient to clean the metal-containing substrate.
 21. The method ofclaim 20, wherein the oxidizer comprises hydroxylamine or ahydroxylamine derivative having the formula:

wherein R₁ is hydrogen or a linear, branched, or cyclic hydrocarboncontaining from 1 to 7 carbon atoms, and wherein X and Y are,independently, hydrogen or a linear, branched, or cyclic hydrocarboncontaining from 1 to 7 carbon atoms, or wherein X and Y are linkedtogether form a nitrogen-containing heterocyclic 4- to 7-membered ring.22-23. (canceled)
 24. The method of claim 20, wherein the salicylic acidcompound comprises salicylic acid.
 25. The method of claim 20, whereinthe oxidizer is hydrogen peroxide.
 26. The method of claim 20, whereinthe oxidizer is periodic acid.
 27. The method of claim 20, wherein theoxidizer comprises persulfide.
 28. A method of post-etch residue removalfor a metal-containing substrate comprising the steps of: contacting ametal-containing substrate that has previously been etched with acomposition comprising: an oxidizer; a salicylic acid compound havingthe formula:

where R₁ and R₂ are independently hydrogen, an organic salt/counterion,an inorganic salt/counterion, a C₁-C₂₀ linear or branched, saturated orunsaturated, optionally singly or multiply substituted alkyl moiety, aC₅-C₂₀ optionally singly or multiply substituted aryl or heteroarylmoiety, or a combination thereof, and where R₃ is a hydrogen, a C₁-C₂₀linear or branched, saturated or unsaturated, optionally singly ormultiply substituted alkyl moiety, a C₅-C₂₀ optionally singly ormultiply substituted aryl or heteroaryl moiety, or a combinationthereof, and wherein optionally substituted moieties comprise hydroxyls,nitro groups, sulfates, phosphates, amines, amides, carboxylic acids,carboxylate salts, carboxylate esters, halides, alkyl or aryl ethers,C₁-C₆ linear or branched, saturated or unsaturated alkyl groups, C₅-C₁₂aryl groups, or the like, or a combination or reaction product thereof;and water, wherein the contacting occurs at a temperature and for a timesufficient to remove post-etch residue from the metal-containingsubstrate.
 29. A method for cleaning and/or removing residue from ametal-containing substrate that has previously beenchemically-mechanically polished, etched, or both, the methodcomprising: contacting the previously treated metal-containing substratewith a composition that comprises from about 0.00001M to about 0.5M of asalicylic acid compound having the formula:

where R₁ and R₂ are each independently hydrogen; an organicsalt/counterion; an inorganic salt/counterion; a C₁-C₂₀ linear orbranched, saturated or unsaturated, optionally singly or multiplysubstituted alkyl moiety; a C₅-C₂₀ optionally singly or multiplysubstituted aryl or heteroaryl moiety; or a combination thereof, andwhere R₃ is hydrogen; a C₁-C₂₀ linear or branched, saturated orunsaturated, optionally singly or multiply substituted alkyl moiety; aC₅-C₂₀ optionally singly or multiply substituted aryl or heteroarylmoiety; or a combination thereof, wherein optionally substitutedmoieties comprise hydroxyls, nitro groups, sulfates, phosphates, amines,amides, carboxylic acids, carboxylate salts, carboxylate esters,halides, alkyl or aryl ethers, C₁-C₆ linear or branched, saturated orunsaturated alkyl groups, C₅-C₁₂ aryl groups, or the like, or acombination or reaction product thereof, and wherein the salicylic acidcompound is present in an amount sufficient to substantially inhibitcorrosion; and water, wherein the contacting occurs at a temperature andfor a time sufficient to clean and/or remove residue from the previouslytreated metal-containing substrate.
 30. The method of claim 29, whereinthe metal-containing substrate comprises a copper-containing substrate.31. The method of claim 30, wherein the copper-containing substrate alsocomprises a tantalum-containing layer.
 32. The method of claim 29,wherein the composition fuirther comprises an organic acid other thanthe salicylic acid compound.
 33. The method of claim 29, wherein thesubstrate is a semiconductor base material.
 34. The method of claim 29,wherein the salicylic acid compound comprises acetylsalicylic acid. 35.The method of claim 20, wherein the oxidizer comprises persulfates,organic and inorganic peroxides, oxidized halides, periodic acid,permanganates, chromates, cerium compounds, ferricyanides, orcombinations thereof.
 36. The method of claim 29, wherein the oxidizercomprises a hydroxylamine or a hydroxylamine derivative having theformula:

wherein R₁ is hydrogen or a linear, branched, or cyclic hydrocarboncontaining from 1 to 7 carbon atoms, and wherein X and Y are,independently, hydrogen or a linear, branched, or cyclic hydrocarboncontaining from 1 to 7 carbon atoms, or wherein X and Y are linkedtogether form a nitrogen-containing heterocyclic 4- to 7-membered ring.37. The method of claim 29, wherein the metal-containing substratecomprises a ferroelectric material, a magnetic material, or both. 38.The method of claim 20, wherein the amount of oxidizer present is fromabout 0.01% to about 30% by weight.
 39. The method of claim 20, whereinthe salicylic acid compound is present in an amount from about 0.01% toabout 5% by weight.
 40. The method of claim 36, wherein the oxidizercomprises hydroxylamine, N-methyl-hydroxylamine,N,N-dimethyl-hydroxylamine, N-ethyl-hydroxylamine,N,N-diethyl-hydroxylamine, hydroxylamine nitrate, hydroxylamine sulfate,hydroxylamine phosphate, or a combination thereof.
 41. The method ofclaim 20, wherein the composition further comprises at least one of thefollowing: a film-forming agent other than the salicylic acid compound;a surfactant; a Theological control agent; a polymeric stabilizer; asurface active dispersing agent; or a combination thereof.
 42. Themethod of claim 41, wherein the total amount of surfactant andrheological control agent present is collectively from about 0.05% toabout 4% by weight.
 43. The method of claim 20, wherein the compositionis substantially free of oxidizers other than hydroxylamine or aderivative thereof, and wherein the composition is substantially free offilm-forming agents other than the salicylic acid compound.
 44. Themethod of claim 29, wherein the composition is substantially free ofcorrosion inhibiting agents other than the salicylic acid compound.